ATOMIC STRUCTURE 6 John Dalton 1801, believed that mater is made up of extremely minute indivisible particle, called atoms. J.J. Thomson 1897, produced cathode rays by passing electric discharge through gas at low pressure. Cathode rays consists of electrons. Production of cathode rays show that atom contains electrons. The properties of cathode rays are (a). They travel ina straight line with high velocity and cast shadow. (b)_ They cause rotary motion, (©). They produce fluorescence when strike the glass walls of dischage tube, coated with ZnS (@)_ They are deflected from straight path by electric and magnetic field which shows hat they consits of minute particles electron carrying — ve charge. From the analysis of anode rays or positive rays; also produced during the production of cathode rays; itis possible to show that the lightest positive particle in the atom is proton. Since atom is electrically netural hence ‘number of protons is equal to number of electrons. Rutherford’s Experiment : In 1911, Rutherford observed that when a-particles emitted from Radium struck thin metalic sheets, many of them passed through the sheet with no change in their path but a few of them got deflected hrough 90° or through larger angles. He concluded that (a) As most of the a-partiles passed underflected, the atom must predominantly consists of empty speae. (0) Asa few ocparticles carrying +ve charge are strongly deflected there mus be a heavy +ve charged body’ present in each atom and the volume occupied by ths is only a minute fraction of the total volume of an atom, He called this +vely charged body as nucleus, It is surounded by small negatively charged particles called electrons, at relatively large distances from the nucleus. In order to explain why the electrons do not fll into the nucleus due o elecrostati attraction, Rutherford proposed that elecrons are revolving round the nucleus at high velocities, The eenrifugal force arising from this motion just balances the force of electrosatie traction Objections to Rutherford’s Model : Whenever an electric charge is subjected to acceleration, it emits radiation and loses energy. As a result of ths, the orbit will become smaller and the electrons will drop on the nucleus. This, however, does not happen. Neil's Bohr Atomic Theory (1913): It is based on the following assumptions (a) The electrons moves around the +vely charged nucleus ina cireula orbit, he centripetal foree for this motion is balanced by the electrostatic atraction (b) The electrons can rotate only in certain orbits which are known as stationary or quantized orbits. When the electron moves in these orbits it cannot emit any radiation. (©) The electrons radiates a quantum of energy of frequency v only when it jumps from an orbit of higher ‘energy to an orbit of low energy. IPE, and E, are the eneries of the electron in two successive orbits, then 1 (hePlanck’s constant) c=3 « 10!” cms, 2 = wavelength The energy of the electrons in an orbit is cabracterised by quantunm number ‘n rrsaios 2Wheren, Z-atomic number; m and ¢ are mass and charge of the electron respectively. The radius of the paths in which can electron can revolve is given by sy 20537 A, GemeZ (A= 10 em) When an clectron jumps from an outer orbit in which its quantum number is “n, the energy emitted as radiation is given by : ton inner orbit in which its *n,"; = 2n'Zie'm be here R is the Rydberg constant. For hydrogen, R is 109677.8 ent! We can concluded two important points from Bohr model (a) The model correctly fits the quantized energy level of the hydroen atom as infered from, its emission spectrum, These energy level correspond o certain allowed circular orbitas for the electrons, (b) As the electron becomes more tightly bound, its energy becomes more negative relative to the zero energy reference state (corresponding to the electron being an infinite distance fom the nucleus) ie as the electron is brought closer to the nucleus, enegy is released from the system. (©) A general equation for the electron moving from one level (na, 10 another level (ng, AE = energy of level My — energy of level Mies = Egat ~ Ei carma09(£)-eres0n/, =-anreciom{ 8. Modern structure of Atom : Atom consists of two parts (A) Nucleus (B) Extra nuclear particles called electrons. (A) Nucleus : The nucleus of an atom has a radius of about 10° cm whereas the atomic radius is about I< 1*em, The nucleus contains different kinds of particles known as nuclear particles or nucleon. The various nuclear particles are as follows = (a) Proton (Hor p): The characteristics of a proton are as follows (Absolute mass = 1.66 « 10 (il) Relative mass = 1 amu (ii) Relative charge = + 1 unit (iv) Absolute charge = + 1.6 x 10°” coulomb = + 4.8 x 10" es. (%) Atomic number = + 1 (i) Inventor : Goldstein in 1886 in “anode Rays Experiments” (b) Positron (¢') (tis an antiparticle of electron because it has same negligible mass and same amount of charge as of the electron but he charge is +ve.Gi) Absolute mass = 9.1 107% g 1 (ii) Relative mass we™ (iv) Relative cahrge= + 1 unit (v) Atomic number = + 1 (9a) Inventor: Wilson in 1927 in his “Cloud Chamber Experiment”. (c) Positive meson (m*) (0 Relative mass = (200 0 300) * 5 Relative charge = + 1 )) Atomic number = +1 (iv) Inventor : C, Anderson in 1939 in “Cosmic Rays Experiment”, (d) Negative meson (x) 1 (i) Relative mass (200 to 300)x cam Relative chage =~ 1 unit )) Atomic number =~ 1 unit (iv). Invenor : C. Anderson in 1947 in “Cosmic Rays Experiments”, (e) Neutron (n) (i) Relative mass = 1.0083 amu Relative charge = zero )) Atomic number = zero (iv) Inventor : J. Chadwick in 1932 by bombading Lithum and Beryllium metals with a-particles. (Neutrino (Relative mass : Variable mass less than that of an electron, Relative charge = Zero )) Inventor: Allen and Rodebeck in 1952, (g) Antiproton (p”) (Relative mass = To that of a proton, (ii) Relative chage = Negative. (ii) Inventor : Segree in 1956. (B) Extra Nuclear Particles; “Electrons” : The electrons can be discussed under following poi (a) Characteristics of electron (€°) : These are as follows : (Absolute mass = 9.11 « 10g 1 Gi) Relative mass = F=zamu (i) Absolute charge =~ 1.6 * 10" coulomb =~ 4.8 10-" es. (iv) Atomie number =~ 1 (v)_ Inventor : JJ. Thomson in 1897 in “Cathode-Rays Experimnent”, Charge wi) ‘ot ~ ratio of electron was first measured by Mulliken in 1909 by means of “Oil-drop Mass" m Experiment”. (a) Principal quantum no. ‘a’ : It represents the distance between electron and nucleus, ie he main energyshell in which particular electron is present. It mainly decides the energy of the electron in the orbit. It also ives the no. of electrons that may be accomodated in each shell. The capacity of each shell being given as 2n, It decides the size of the shell. mre 2n'mZey cs E = Energy of electron in a particular level, Electron charge, m= Mass of electron, Z_= Atomic number, h = Planck’s constant. E (b) Azimuthal or secondary or subsidiary quantum number ‘I’: It represents the no. of subshells can have the values 0 to (1. 1). It gives the shape of he subshell ‘The volume of space where probability of finding an electron is maximum, is called orbital or subshell. Properties: s P a f 8 shape Spin Dumb-bell Double Complicated S dumb-bell No. of sub- subshells 1 3 5 1 0 1 2 3 4 Max. no.of 2 6 10 4 Is electrons cone AST y apy y y MS 4, dy 4, dy 4, (©) Magnetic quantum no, ‘m’: This gives he no. of orbitals in a subshel (ander the influence of magnetic field). It takes only integral values rom | to +1 through zero m=21+1 for any value of , © 1=0m-1 In s-subshell there is only one sub-subshell {In p-subshell there are p, p, p, where x, y, z refer to the axis perpendicular to each other Ind-subshell there are ddd, dey and d.. In Fsubshell there are 7 orbital. (@) Spin quantum no. *s* : When an electron rotates around a nucleus, it spins around its axis. It spin os \ \ cocks its writen a as +r? Ianto shen itis —Eor (een na. 6)2m ‘We can write allowed combinations of quantum numbers for the first four shells as below ayt m ‘Orbital ‘Number of | Number of rotation orbitals in orbitals in subshell shell T[o oO Ts 1 A 21° 0 2s 1 4 1 -1+1 2p. 3 0 0 38 T 9 3.4 “1,0, 41 3p 3 2 104142 3d 5 0 0 4s 1 16 ai -1,0,+1 4p 3 2] -2-1,0,41,42 ad 3 3 2, -1,0,+1,42,43 af a (D) The Quantum Mechanical Description of the Atom ‘ co) dde-Brogle’s theory : Bohr reated electron as a paticle, However, de Broglie suggested that electron has a dual nature, ie. it behaves both as a particle as well as wave. The wavelength 2 ofa moving particle v and m are the velocity and mass of moving particle respectively. If r is radius of the wave, 2x it circumference, then an=2nr (2) Thus, according to wave theory an electron is a stationary wave moving around the nucleus in a circular path. The wave characier was later on conformed by Davison Germer (1927) and Thomson (1928). From eq, (1) and (2), we have ah ah 2nr =" or mvr == mv 2 According to Schrodinger, the electron does not move round the nucleus in fixed orbits, but may, infact, be anywhere with different probabilities. The probability of its presence near the nucleus is greatest and as the distance from nucleus increases the probability decreases. Schrodinger from mathematical treatment of wave motion gave a general wave equation describing the behaviour of a small particle. Consider a system such as a stretched string. For its vibration. 2nx = Asin : x Where, x = displacement, ¥ = wave function, A= amplitude of the wave, = wavelength ae scm ; (E-PE)y "for an electron at a given point indicates the probability of occurrence of the electron at that point If above equation is solved by Y several solutions are found. Among those solutions, the solutions which are single valued and containuous function are permitted solution. They are called as eigen functions.(a)_radialnode or spherical node : number of radialnode (b) Angular node or nodal plane : no. of Angular node Total node =n-1—1+1=n—1 (ii) Heisenber’g uncertainty principle : It states “It is impossible to determine simultaneously both the psoition and the velocity of a moving electron”. Let Ax be the uncertainty in determining its position and Ap the uncetaintly in determining its momentum at the same time then according to Heisenberg principle in case of electron, the product of uncertainty of velocity and position is propportional to Planck's constant and can never be less than 2a RULES FOR FILLING OF ELECTRONS IN THE ORBITAL(S) There are three rules 4. THe Auraau PRINCIPLE According to it an electron enters the orbital that has the minumum energy. AAs protons are added one by one to the nucleus to build up the elements, electrons are similarly added to these atomic orbitals. The energy of different atomic orbitals is as follows, B® Thus the inereasing order of energy is Is > 28 > 2p > 38 > 3p 9 4s 93d > dp 95s > dd > Sp —> 6s > 4F > Sd > Gp > SF 6d > Ip 2._Huno's Rute It states that electron pairing in any s, p, d or Forbital is not possible unit all the available orbitals of the same “orbital contain one electron each. It means an electron occupies a vacant orbit in the same orbital and pairing can start when all the orbitals are filled up. Pairing occurs only after filling 3, 5 and 7 electrons in p, d and f-orbitals, respectively. For example, the configur of carbon atom may be written as =ce: [AIIM ftTt Is 28 2p Similarly for nitrogen may be written as Ne TN] [MI LET tt Is 28 2p Likewise for oxygen : o: [HN] LM] tt in a ap PAUL! EXCLUSION PRINCIPLE It states that no two electrons in an atom can have all the four quantum number identical. In other words, ‘maximum number of electrons in an orbital can be two with opposite spin. For example, the value (s) of the quantum number (s) 11th and 12th electron of magnesium is as follows 1th eleetron ; ),m=0,s=+ 12th electron ; ATOMIC SPECTRA ‘When the sunlight is passed through prism, itis dispersed into 7 colour which is called as spectra. Ifthe atom is, excited and then examined through spectroscope. We see no. of lines. This is called line spectra or atomic spectra. Atomic spectra of hydrogen Bohr (1913) proposed that an electron moves only in the orbit in which angular momentum of the electron is equal ‘When an electron jumps from one orbit to anoher it either loses or gains energy in he form of radiation, The energy of radiation is given by = E,-B,=hv . en ‘Therefoe line in the spectrum of *H’ results from the dropping of electron excited to hiher stationary states back to lower, or less energetic states. Each line was ascribed to a transfer to the electron from an orbit of some nvalue to an obit of some lower n value. Using this, Bohr was able to account for the observed wavelength of the lines in Lyman, Balmer and Paschen series. Balmer (series is found in) visble. Paschen near infra-red, Brackett far infra-red, fund Lyman Balmer far infra-red Paschen T T 200A 400A. 600A $00A. 180A Wavelengths of these series were determined from he following expression, where Rj, = Rydberg’s constanat for Lyman for Blamer =3 for Paschen = 4 for Brackett 5 for Pfund It failed to systems conaining more than on electron. The hydrogen atom It can be discussed as below (a) In quantum mechanical model the electron is described as a wave. Thsi representation leads to a series of ‘wave functions (orbitals) that describe the possible energies and special distributions available to the electorn. (b) In agreement with the Heisenberg’s uncertainty principle, the model cannot specify the detailed electron ‘motons. nstead, the square of the wave function represents the probability distribution of the electron in that orbital. This approach allows us to picture orbitals in terms of probability distributions, or electron density ‘maps. (©) The size of an orbital is arbitarily defied as the surface that contains 90% of the total electron probability. (@)_ The hydrogen atom has many types of orbitals. n the ground state the single electron resides in the Ist orbital. The electron can be excited to higher energy orbitals if the atom absorbs energy. Few Terms (a) Mass Defeet : Actual mass of atom is not equal to the sum of mass of e, p and n present init, ex for chlornie 1sClS = 17 (1.007276) amu + 18(1.008665) amu + 17.(0.0005486) amu = 35.289005 amu However, the mass of chlorine has been accurately determined as 34,96885 amu. This difference between the two values (35.28901 amu ~ 34.96885 amu) = 0.32016 amu is known as mass defect. This difference, expressed in its energy equivalent, is called the binding energy of the nucleons (neutrons * protons) in the nucleus of the atom in questions (b) Isotopes : Atoms of an element havnig the same atomic no., but different at. wt. are called isotopes. eg. SCland Cl 1H, ;Dand }T; "0, ?Oand "0 Isotopes have the same no. of protons and electrons but different no. of neutrons. They have the same chemical properties. The fractional at. wt. of an clement is due to the different proportion in which vaious© ©) chlorine has two isotopes ,,CI® and CE” present in the ratio 3 : 1 isotopes are present in it 3335-4137 Average at wt =35.Samu Tobars : Atoms having the same no. of neutrons but different no, of protons are called isotones, Si, uP Isoelectronic ions or Molecules : Species having same no, of electron but different charge of nucleus are known as Isoeleetronie ions, e. (OF Ne,Na’, Mg", AP (i) NO, CO,” cocl, Gi) NHI, 10° (iv) Ny, CO, CN (v) NCS and Cs, (vi) IF He, Li Isodiaphers : Atoms having same isotopic numbers. ie. same value of (n-p) but different atomic as well as mass number.